1. Field of the Invention
The present invention relates generally to methods of preparing hybrid “organic-inorganic” chemical compositions that are wholly useful by themselves or in combination with other comonomers for producing novel polymeric compositions with desirable physical properties such as adhesion to polymeric, composite and metal surfaces, water repellency, low dielectric constant, resistance to abrasion and fire, biological compatibility, and optical quality plastics. The new compositions reported herein contain two primary material combinations.
Part one of the combination is a silicon component which may be comprised of a silane, silicone, silsesquioxane, polyhedral oligomeric silsesquioxane, silicate, polyhedral oligomeric silicate or combinations thereof. The silicon-component provides chemical oxidation resistance, thermal stability, and structural reinforcement to the overall molecule. The second component of the composition is one or more ring strained olefinic groups. The ring strained olefinic groups provide the primary reactive functionality for polymerization and for solubilization. The ring strained olefin may be comprised in whole or part from primarily olefinic carbon-based rings (e.g. cyclo-propyl, butenyl, pentenyl, hexenyl, norbornenyl). In some cases one or more hetero atoms such as N, O, S, P, B may also be included in the strained olefinic ring (e.g. ring strained cyclic olefinic imides or ethers).
2. Brief Description of the Prior Art
Prior art has demonstrated that strained olefinic rings can be utilized in polymerizations using free radical and UV initiators and transition metal based catalysts. See Haddad et al., J. Amer. Chem. Soc. Polym. Preprints Vol 38, No 1. 1997, pp 127-128, and Mather et. al. Macromolecules Vol 32, (1999), pp 1194-1203 (utility of POSS-polynorbornenes); G. Odian, Principles of Polymerization, 3rd Ed. John Wiley & Sons, (1991) p 578 (polynorbornenes and their utility). Prior art by Tenney et al in U.S. Pat. No. 5,190,808 described the use of silane-substituted monomers containing only one strained ring olefin, per silicon, for the preparation of prepregs for the construction of printed circuit boards. This art was limited in scope and conception and did not fulfill the need for the development of other silicon based strained ring olefin systems that could serve as crosslinkers and zero volatile organic comonomers or as resin systems for use in the manufacture of electronic, medical, sporting goods, aerospace and automotive components, packaging and personal care products. Prior art by Leibfried in U.S. Pat. No. 4,900,779 reported the process of using the hydrosilation of hydridosilanes and strained ring olefins for the purposes of forming crosslinked network materials having tailorable physical properties. Leibfried does not teach methods that allow for the preparation and isolation of silicone, silane, polyhedral oligomeric silsesquioxane or polyhedral oligomeric silicates that bear olefinic strained rings. Nor did they teach the use of such isolable intermediate species for subsequent utility in ROMP polymerizations. Leibfried was also silent as to the usage of silation as method of preparing such materials rather only a hydrosilation method was taught for the attachment of the strained olefinic group to the silane silicon atoms. Literature by Hambley et al. report the preparation of silsesquioxane materials bearing a norbornyl functionality for the purposes of steric bulk and solubility. They did not utilize a strained ring olefinic type of norbornene group and they did not teach the use of such a derivative for polymerization purposes. See Hambley, et al., Applied Organometallic Chemistry (1992) Vol 6 No. 3, pp 253-260.